N - (1- or 2 - (4,5,6,7,8,9 - hexahydro - 4,7 - methanoindanyl)) - n&#39;,n&#39; - dimethyl urea and use in weed control



3,365,289 N or 2 3,56,733 HEXAHYDRG 4,7 METH- ANGHNDANYL); NQN DIMETHYL UREA AND it T 'ivTtED ECQNTRGZL Paul Rafi Ludwig Schuster, Ludwigshafen (Rhine), Adoif Fischer, Mutterstadt, Efaiz, Guenther Scheuerer, Ludwigshaien (Rhine), and Gustav Steinbrunn, Schwegenheim, Pfalz, Germany, assignors to Badische Aniliri- Soda-Fabrik Ahtiengeseilschaft, Ludwigshafen, (Rhine), C ea-many No Drawing. Filed .ian. 19, 1965, Ser. No, 426,664 priority, application Germany, Jan. 24, 1964,

B 75,134 2 Claims. (Ci. 71-120) ABSTRACT @31 THE DTSCLGSURE Herbicide compounds which are N-[lor 2-(4,5,6,7,8, 9-hexahydro-4,7-rnethanoindanyl)]-N-dimethyl ureas of the formula below and uses thereof in weed control.

The present invention relates to urea derivatives, and more particularly to urea derivatives having selective herbicidal action. These urea derivatives are suitable for controlling weeds without damaging corps.

We have found that compounds having the formula in which R denotes a methyl group having a good herbicidal action. it is immaterial for the herbicidal action whether the tricyclic hydrocarbon radical bears substituents in 1- (or 3-) or 2-position. Since the arrangement of the various individuals to the various formulae of the isomers has not yet been clarified, the following urea derivatives are characterized by their physical constants and listed as active substances:

N-[ 1- or 2-(4,5,6,7,8,9 hexahydro 4,7 methanoindanyl)]-N'-dirnethylurea; melting point 154 to 156 C.

N-[Z- or l-(4,5,6,7,8,9 hexahydro 4,7 methanoindanyl)]-N-dimethylurea; melting point 202 to 203 C.

The ureas may be prepared analogously to known methods by reaction of appropriate isocyanates with the appropriate amines in inert or aqueous solvents, or from the amines with the appropriate carbamic acid derivatives dissolved in a hydrocarbon and in the presence of an acidbinding agent or a catalyst.

Appropriate amines are obtained as mixtures of isomers by reacting 4,5,6,7,8,9-hexahydro-4,7-methanoindene with hydrocyanic acid in the presence of sulfuric acid and subsequent hydrolysis of the resultant formarnide. The following equations illustrate the possibilities of preparation:

States Patent 3,365,239 Patented Jan. 23, 1963 in which R has the meanings given above and X denotes halogen, alkoxy or phenoxy.

The compounds may be used alone or mixed with other herbicidal active substances, as for example urea derivatives, triazines, pyridazone derivatives, carbamates, thiocarbamates, uracil derivatives or borates. The rate of application is from about 1 to 10 kg. of active substance per hectare.

The agents according to this invention may be prepared by mixing the urea derivatives with conventional solid or liquid carrier substances, for example fertilizers, inert solid carrier substances, talc, diatomaceous earth, water, organic liquids, xylene, petroleum distillates or synthetic organic liquids.

The following examples illustrate the use of the agents according to this invention.

EXAMPLE 1 Barley (Hordeum vulgare), beet (Beta vulgaris), cotton (Gossypium spp.), rice (Oryza sativa), wild oats (Avena fcztzza), slender foxtail (Alopecurus myosuroides), annual meadow grass (Poa annua), White mustard (Sinapis alba) and a mixture of Weeds consisting of chickweed (Stellarz'a media), small nettle (Urtica urens), common goosefoot (Chenopodium album), camomile (Matricaria chamomilla), storks bill (Geranium), amaranth (Amaranthus rezroflexzzs) and tares (Vicz'a) are sown in plastic pots having a diameter of 8 cm. in a greenhouse. Immediately thereafter 2.5 kg. of active substance (N-[lor 2(4,5,6, 7,8,9 hexahydro 4,7 methanoindanyD] N'-dimethylurea, melting point 154 to 156 C.) per hectare dispersed with sodium lignin sulfonate in an amount of water equivalent to 500 liters per hectare is sprayed onto the surface of the soil. The plants at first develop normally but about eight days later begin to wither from the leaf tips. Two to three weeks later, beet (Beta vulgaris), slender foxtail (Alopecurus myoszrroz'des), wild oats (Avena fame), annual meadow grass (Poa annua), white mustard (Sinapis alba) and the weed mixture have almost completely withered, whereas rice (Oryza sativa), barley (Hordeum vulgare) and cotton (Gossypium spp.) continue to grow without damage.

EXAMPLE 2 Barley (Hordeum vulgare), beet (Beta vulgaris), cotton (Gossypium spp.), rice (Oryza sativa), slender foxtail (AIopecm-us myoszzroides), wild oats (Avena fatua), annual meadow grass (Poa annua) and white mustard (Sinapis alba) are sprayed in the greenhouse, after they have reached a growth height of 4 to cm., with N-[lor 2-(4,5,6,7,8,9-hexahydro-4,7-methauoindanyl)]-N'-dimethylurea (melting point 202 to 203 C.) in an amount corresponding to a rate of application of 2 kg. of active substance per hectare dispersed with sodium lignin sul- 7 fonate in an amount of water equivalent to 500 liters per hectare.

Some days later, the plants begin to wither from the leaf tips and tWo or three weeks later the beet (Beta vulgaris) is severely damaged and rice (Oryza sativa) only slightly damaged. Slender foxtail (Alopecurus myosuroides), wild oats (Avena fatua), annual meadow grass (Poa annua) and White mustard (Sinapis a'lba) are almost wholly destroyed, whereas cotton (Gossypium spp.) and barley (Hordeum vulgare) continue to grow Without damage.

We claim: 1. A compound of the formula:

5 the formula:

CF13 /C{ /Cgz/NHCON CH2 CH CH3 0112 CH1 CH2 I CH CH CH2 References Cited UNITED STATES PATENTS 10/1966 Richter 'il2.6

HENRY R. JILES, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,365,289 January 23, 1968 Paul Raff et a1.

It is certified that error a patent and that said Letters Pate shown below:

ppears in the above identified nt are hereby corrected as Column 2, the portion of the second formula reading Signed and sealed this 25th day of November 1969.

LEAL) ttest:

[ward M. Fletcher, Jr.

WILLIAM E. SCHUYLER, JR. testing Officer Commissioner of Patents 

